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The barrier energies for isomerization and fragmentation were measured for a series of retinal chromophore derivatives using a tandem ion mobility spectrometry approach. These measurements allow us to quantify the effect of charge delocalization on the rigidity of chromophores. We find that the role of the methyl group on the C13 position is pivotal regarding the ground state dynamics of the chromophore. Additionally, a correlation between quasi-equilibrium isomer distribution and fragmentation pathways is observed.

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We describe the design of and the first commissioning experiments with a newly constructed electrostatic storage ring named SAPHIRA (Storage Ring in Aarhus for PHoton-Ion Reaction Analysis). With an intense beam of Cu(-) at 4 keV, the storage ring is characterized in terms of the stored ion beam decay rate, the longitudinal spreading of an injected ion bunch, as well as the direct measurements of the transverse spatial distributions under different conditions of storage. The ion storage stability in SAPHIRA was investigated systematically in a selected region of its electrical configuration space.

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The fragmentation, initiated by photoexcitation as well as collisionally-induced excitation, of several retinal chromophores was studied in the gas phase. The chromophore in the protonated Schiff-base form (RPSB), essential for mammalian vision, shows a remarkably selective photoresponse. The selectivity of the gas-phase chromophore is triggered by a series of fast trans to cis isomerizations followed by a Diels-Alder cyclization with subsequent slow statistical fragmentation, leading to one specific fragment ion. The pattern of the final statistical fragmentation may be altered by chemical modifications of the chromophore. We propose that isomerizations play an important role in the photoresponse of gas-phase retinal chromophores and guide internal conversion through conical intersections. The role of protein interactions is then to control the specificity of the photoisomerization in the primary step of vision and possibly to diminish thermal noise by suppressing spontaneous isomerization by heat.

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We describe a technique to measure absolute photo-induced cross sections for cluster anions stored in an electrostatic ion beam trap (EIBT) with a central deflector. The setup allows determination of total photo-destruction cross sections as well as partial cross sections for fragmentation and electron detachment. The unique properties of this special EIBT setup are investigated and illustrated using small Al(n)(-) clusters.

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Photoelectron spectra of the deprotonated green fluorescent protein chromophore have been measured in the gas phase at several wavelengths within and beyond the S(0)-S(1) photoabsorption band of the molecule. The vertical detachment energy (VDE) was determined to be 2.68 ± 0.1 eV. The data show that the first electronically excited state is bound in the Franck-Condon region, and that electron emission proceeds through an indirect (resonant) electron-emission channel within the corresponding absorption band.

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Photodissociation lifetimes and fragment channels of gas-phase, protonated YA(n) (n = 1,2) peptides and their dimers were measured with 266 nm photons. The protonated monomers were found to have a fast dissociation channel with an exponential lifetime of ~200 ns while the protonated dimers show an additional slow dissociation component with a lifetime of ~2 µs. Laser power dependence measurements enabled us to ascribe the fast channel in the monomer and the slow channel in the dimer to a one-photon process, whereas the fast dimer channel is from a two-photon process. The slow (1 photon) dissociation channel in the dimer was found to result in cleavage of the H-bonds after energy transfer through these H-bonds. In general, the dissociation of these protonated peptides is non-prompt and the decay time was found to increase with the size of the peptides. Quantum RRKM calculations of the microcanonical rate constants also confirmed a statistical nature of the photodissociation processes in the dipeptide monomers and dimers. The classical RRKM expression gives a rate constant as an analytical function of the number of active vibrational modes in the system, estimated separately on the basis of the equipartition theorem. It demonstrates encouraging results in predicting fragmentation lifetimes of protonated peptides. Finally, we present the first experimental evidence for a photo-induced conversion of tyrosine-containing peptides into monocyclic aromatic hydrocarbon along with a formamide molecule both found in space.

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We report on the realization and operation of a fast ion beam trap of the linear electrostatic type employing liquid helium cooling to reach extremely low blackbody radiation temperature and residual gas density and, hence, long storage times of more than 5 min which are unprecedented for keV ion beams. Inside a beam pipe that can be cooled to temperatures <15 K, with 1.8 K reached in some locations, an ion beam pulse can be stored at kinetic energies of 2-20 keV between two electrostatic mirrors. Along with an overview of the cryogenic trap design, we present a measurement of the residual gas density inside the trap resulting in only 2 x 10(3) cm(-3), which for a room temperature environment corresponds to a pressure in the 10(-14) mbar range. The device, called the cryogenic trap for fast ion beams, is now being used to investigate molecules and clusters at low temperatures, but has also served as a design prototype for the cryogenic heavy-ion storage ring currently under construction at the Max-Planck Institute for Nuclear Physics.

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We describe a bent electrostatic ion beam trap in which cluster ions of several keV kinetic energy can be stored on a V-shaped trajectory by means of an electrostatic deflector placed between two electrostatic mirrors. While maintaining all the advantages of its linear counterpart [Zajfman et al., Phys. Rev. A 55, R1577 (1997); Dahan et al., Rev. Sci. Instrum. 69, 76 (1998)], such as long storage times, straight segments, and a field-free region for merged or crossed beam experiments, the bent trap allows for simultaneous measurement of charged and neutral fragments and determination of the average kinetic energy released in the fragmentation. These unique properties of the bent trap are illustrated by first results concerning the competition between delayed fragmentation and ionization of Al(n) (-) clusters after irradiation by a short laser pulse.

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The cross sections for electron detachment of internally cold Cn- and Aln- clusters were measured using an electrostatic ion beam trap fitted with an internal electron target. The measured electron-impact detachment cross sections for the Cn- (n = 1-9) clusters exhibit even-odd oscillations reflecting the binding energy trend, namely, higher cross sections for weaker binding. Surprisingly, however, these cross sections increase on the average with cluster size, n, in spite of the increase in electron binding. In contrast, the Aln- (n = 2-5) clusters follow the known scaling laws for electron detachment. We suggest that the size-dependent polarizability of these clusters is responsible for the observed behavior.

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A case of QT prolongation and ventricular tachyarrhythmia in a 57-year-old patient treated with small therapeutic doses of sotalol is reported. There was no concomitant treatment prolonging the QT interval. Hypokalemia could be excluded. Before treatment an electrophysiological study was performed, and ventricular tachycardia could not be initiated. Coronary artery disease was excluded. QT prolongation and ventricular tachyarrhythmias induced by small therapeutic doses of sotalol in normokalemia may occur on rare occasions. It may be problematic to differentiate between torsade de pointes and polymorphous ventricular tachycardia when describing such a ventricular tachyarrhythmia.

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